Novel organosilicon compounds



United States Patent 3,197,431 NGVEL @RGANUSTLKIGN CUMPQUNDS William M. Lanham, Charleston, and Percy L Smith,

Dunbar, W. Va, assignors to Union tlarbirle Corporation, a corporation of New York No Drawing. Filed Juiy 25, 1%(3, Ser. No. 44,835 25 (Iiaims. (Ql. 260-465) This invention relates to novel organosilicon compounds which contain phosphorus and nitrogen. The compounds of this invention include hydrocarbonoxysilanes and siloxanes containing a phosphinylidyne group [i.e. a group having the formula EP(O)] which is bonded to two hydrocarbonoxy groups and to one nitrogen atom which is also bonded to a hydrocarbonoxysilyl or siloxysilyl group through at least three carbon atoms of a divalent hydrocarbon group. Also included among the compounds of this invention are polymers produced by hydrolyzing and condensing the hydrocarbonoxysilanes and siloxanes of this invention.

The hydrocarbonoxysilanes of this invention are represented by the formula:

wherein R is a monovalent hydrocarbon group, R is a hydrogen atom of a monovalent hydrocarbon group, R is a divalent hydrocarbon group, n is an integer from 0 to 2 inclusive and the nitrogen atom is interconnected to silicon through at least three carbon atoms.

Illustrative oi the monovalent hydrocarbon groups represented by R and R in Formula 1 are the linear alkyl groups (for example the methyl, ethyl, propyl, butyl and stearyl groups), the cyclic alkyl groups (for example the cyclohexyl and cyclopentyl groups, the linear alkenyl groups (for example the vinyl and the allyl groups), the cyclic alkenyl groups (for example the cyclopentyl and the cyelohexenyl groups), the aryl groups (for example the phenyl and naphthyl groups), the alkaryl groups (for example the tolyl group) and the aralkyl groups (for example the benzyl and beta-phenylethyl groups).

Illustrative of the divalent hydrocarbon groups represented by R" in Formula 1 are the linear alkylene groups (for example the trimethylene, -(CH and the octadecamethylene, (CH r groups), the arylene groups (for example the naphthylene, C H and para-phenylene, C H groups); the cyclic alkylene groups (for example the cyclohexylene --C H group); the alkarylene groups (for example the tolylene, CH C H group) and the aralkylene group (for example the CH (C H )CHCH CH group).

The preferred silanes of this invention are those represented by Formula 1 wherein R and R each individually contain from 1 to 18 carbon atoms and wherein R contains at least 3 carbon atoms, and most preferably from 3 to 5 carbon atoms, interconnecting silicon and nitrogen but contains not more than 18 carbon atoms.

Illustrative of the silanes of this invention are:

and

The siloxanes of this invention contain a group represented by the formula:

2 (2) wherein R, R, R" and n have the above-defined meanings and the nitrogen atom is interconnected to silicon through at least three carbon atoms.

Illustrative of the groups represented by Formula 2 are the groups having the formulae:

ii (CH O)zPN(CH2)sSiOm t t s s )2 2)4SiO1.s

ll 2 50) gPl TCuH4SiO The siloxanes of this invention include those siloxanes that are composed solely of groups represented by Formula 2 and also include those siloxanes that contain one or more groups represented by formula 2 together with one or more groups represented by the formula:

wherein R has the above-defined meanings and x has a value from 0 to 3 inclusive.

Illustrative of the groups represented by Formula 3 are: the SiO phenylsiloxy, methylsiloxy, dimethylsiloxy, methylethylsiloxy, trimethylsiloxy, diphenylsiloxy, vinyl (methyl)siloxy, divinylsiloxy, methyldiphenylsiloxy and dicyclohexylsiloxy groups and the like.

The hydrocarbonoxysilanes and siloxanes of this invention are advantageously prepared by reacting a silicon compound (i.e. a hydrocarbonoxysilane or a siloxane) having an amino group interconnected to silicon through a divalent hydrocarbon group with a phosphorus compound composed of a phosphinylidyne group bonded to a halogen atom and to two hydrocarbonxy groups. The reaction is represented by the skeletal equation:

R o R (R0) li"X Hl I-RSiE (R 0) i *1 tR"-sE EX wherein R, R and R" have the above-defined meanings; X is a halogen atom (preferably chlorine or bromine); and the free valences of the silicon atom bond the silicon atom (in the case of silanes) to at least one hydrocarbonoxy group or (in the case of siloxanes) to at least one siloxy group and any remaining free valences of the silicon atom bond the silicon atom to a monovalent hydrocarbon group.

The process is best carried out by forming a reaction mixture of the silicon compound used as a starting material and the phosphorus compound used as a starting material and maintaining the reaction mixture at a temperature at which the desired reaction occurs. The continuous removal from the reaction zone of the hydrogen halide [HX in Equation 4] as it is formed in the reaction is preferred.

The mole ratio of the phosphorus compound and the silicon compound employed in the reaction represented by Equation 4 is not narrowly critical. Stoichiometric amounts, i.e., the relative molar amounts indicated by Equation 4, are preferred for efficient reaction and ease of product recovery. For example, one gram atom of the nitrogen-bonded hydrogen of the silicon compound desired to be displaced is preferred for each gram atom of phosphorus-bonded halogen of the phosphorus compound. The use of no more than stoichiometric amounts of the starting phosphorus compound is especially desirable where R in Equation 4 is a hydrogen atom in order to minimize the production of products having two phosphorus atoms bonded to each nitrogen atom.

The temperature at which the reaction represented by Equation 4 is conducted is not narrowly critical and can be varied in accordance with the speed of reaction desired. Temperatures of C. to 300 C. are advantageous in providing a smooth reaction and high yields of products. Temperatures below 20 C. can be employed if desired but the reaction rate is slowed. Temperatures above 300 C. can also be'employed but the likelihood of reduced yields is greater and the expense of operating at such high temperatures is undesirable. The process is advantageously carried out at atmospheric pressure or at whatever pressures exist in the particular reaction vessel employed without purposely applying increased or reduced pressures (i.e. autogenous pressure). Sub-atmospheric or super-atmospheric pressures can be employed, however, if desired.

No catalysts are required to effect the reaction represented by Equation 4 although suitable catalysts such as tetramethyl ammonium chloride, trimethyl benzyl ammonium chloride and the like can be employed for whatever advantage they may provide. Solvents also are not required but under certain conditions are useful in sirn- V plifying the handling of the reaction mixture or reducing the reaction time by providing a homogeneous reaction mixture if such is not otherwise obtainable. If a solvent is employed xylene, toluene, benzene, methylethyl ketone, dimethyl formamide, and the like can be used. A solvent which dissolves the starting materials and the products but does not dissolve hydrogen halides is particularly useful in removing the hydrogen halides from the reaction zone. Such solvents include toluene, benzene, xylene, dimethyl formamide, and the like.

The hydrogen halide (HX) formed in the reaction represented by Equation 4 is preferably continuously removed from the reaction zone by any suitable method of which many are known. A particularly suitable method is to add to the reaction mixture a hydrogen halide ac- V ceptor in the approximate stoichiometric amounts'based on the amount of hydrogen halide expected to be formed in the reaction. Tertiary amines (e.g., triethyl amine, pyridine,,tributyl amine, and the like) are some of the excellent hydrogen halide acceptors. Such tertiary amines form salts with the hydrogen halide which salts are insoluble in the reaction mixture. of the acceptors over and above the stoichiometric amount is preferably employed to ensure the substantially complete removal of the hydrogen halide. Alternately, the hydrogen halide can be continuously removed by heating Excess amounts the reaction mixture to cause the hydrogen halide to be decreased yields due to possible side, reactions involving the hydrocarbonoxysilanes) can be isolated by filtration to remove insoluble salts and fractional distillation of the filtrate. The relatively high boiling compounds of this invention (i.e., in general the siloxanes) can be isolated by strippingforeign material, extraction, filtering and/or recrystallization. One or more of the various conventional means can be employed to isolate the compounds of this invention.

The phosphorus compounds employed as starting materials in the above-described process for producing the compounds of this. invention are represented by the formula:

. r 0 2i X (5) wherein 'R and X are as previously defined. The preferred starting phosphorus compounds are those wherein R contains'from l to 18 carbon atoms and X is chlorine or bromine.

Illustrative of phosphorus compounds represented by Formula 5 are: (C H O) P(O)Cl, (C H O) P(O)Cl, s )2 1e s7 )2 L G 11 )2 L fi i z nw m (CH -CHO P O C1 The silicon compounds employed as starting materials in the above-described process for producing the compounds of this invention include both hydrocarbonoxysilanes and siloxanes that contain an amino group interconnected to silicon through a divalent hydrocarbon group. The hydrocarbonoxysilanes used as starting materials in producing the hydrocarbonoxysilanes of this invention are represented by the formula:

wherein R, R, R and n; have the above-defined meanings and the nitrogen atom is interconnected to silicon through at least three carbon atoms. Illustrative of these silanes are gamma-aminopropyltriethoxysilane, para-aminophenyltrimethoxysilane, I delta-aminobutyl(diphenyl)ethoxysilane, epsilon-aminopentyl(methyl)dipropoxysilane, N- propyl-para-aminophenyl(ethyl)dimethoxysilane, N-ethyl-gamma-aminopropyltriethoxysilane, delta-aminobutyltripropoxysilane, para aminophenyl(methyl)diethoxysilane' and thelike.

The siloxanes that are used as starting materials in producing the siloxanes of this invention contain a grou that is represented by the formula:

wherein R, R, R and nhave the above-defined meanings and the nitrogen atom is interconnected to silicon through at least three carbon atoms. Illustrative of the groups represented by Formula7 are the gamma-aminoproylsiloxy, para-aminophenylsiloxy, delta-aminobutyl(diphenyl)siloxy, epsilon-aminopentyl(methyl)siloxy, N-propyL para-aminophenyl( ethyl siloxy, N-ethyl-gammaaminopropylsiloxy, delta-aminobutylsiloxy and para-amino phenyl(methyl)siloxy groups and the like.

Suitable starting siloxanes include both those silox'anes that are composed solely by groups represented by Formula 7 and those siloxanes that contain one or more groups represented by Formula 7 together with one or more groups represented by Formula 3.

The polymers of this invention that are produced by hydrolyzing and condensing the hydrocarbonoxysilanes and siloxanes of this invention contain a group that is represented by the formula:

o R an il l wherein R, R, R", and n have the above-defined meanings. In such groups the phosphorus atom provides a link in the polymeric chain.

The silicon atom in the group represented by Formula 8 can be linked through oxygen only to silicon or phosphorus or can be linked through oxygen to both silicon and phosphorus of another group or groups represented by Formula 8 to provide links in the polymeric chain. The phosphorus atom in Formula 8 can be linked through oxygen only to silicon or phosphorus or can be linked through oxygen to both silicon and phosphorus of another group or groups represented by Formula 8 to provide links in the polymeric chain. Such polymeric chains can be cyclic or can be terminated by hydroxyl or hydrocarbonoxy groups linked to a silicon atom or to the phosphorus atom. Such polymeric chains can also be terminated by an R SiO group linked to a silicon atom in the group represented by Formula 8.

When the phosphorus atom in a group represented by Formula 8 is linked through oxygen to silicon atoms of other groups represented by Formula 8, the groups so linked can be depicted (in the case where n is 2) by the formula:

wherein R, R and R" have the above-defined meanings.

When the phosphorus atom in a group represented by Formula 8 is linked through oxygen to phosphorus atoms of other groups represented by Formula 8, the groups so linked can be depicted (in the case where n is 2) by the wherein R, R and R" have the above-defined meanings.

Illustrative of the polymers of this invention that contain a group represented by Formula 8 are the polymers that are produced by the hydrolysis and condensation of the silane:

Such polymers are composed of the groups having the formula:

The hydrolysis and condensation reactions whereby polymers containing groups represented by Formula 8 are produced involve the reaction of a hydrocarbonoxysilane or a siloxane of this invention with Water to hydrolyze the POR groups, and, if any, SiOR groups in the former compounds to form POH group and SiOI-I groups which condense to form the polymer. The amount of water employed in the hydrolysis and condensation is at least one mole for each mole of SiOSi, Si-OP and P-OP linkages desired to be produced (i.e., one mole of water for each two moles of silicon-bonded and/or phosphorus-bonded hydrocarbonoxy groups desired to be hydrolyzed to form silicon bonded hydroxyl groups which condense with each other to form the Si-OSi, SiOP or P-O-P linkages). A small excess of water over and above this amount is preferred for speed and ease of reaction. Of course, silicon-bonded and phosphorus-bonded hydrocarbonoxy groups can be present in the polymer, if desired, by incompletely hydrolyzing the silicon-bonded and phosphorus-bonded hydrocarbonoxy groups by using lesser amounts of water. Silicon-bonded and phosphorus-bonded hydroxyl groups can be present in the polymer if desired, by incompletely condensing the hydroxyl groups formed by hydrolysis. Such incomplete condensation is effected by using a large excess of water and short reaction times in the hydrolysis and condensation.

The hydrolysis and condensation reactions whereby are produced polymers containing groups represented by Formula 8 can be conducted at temperatures from 0 C. to 250 C. Temperatures in the range of about 50 C. to C. are preferred in order to hasten the hydrolysis and condensation without thermal decomposition. A solvent is preferably employed to provide ease of han dling the reaction mixture. Suitable solvents are the liquid hydrocarbon-s '(e.g.,' toluene, benzene, xylene and the like), alcohols (e.g., ethanol, iso-propanol and the like) and ethers (e.g., di-isopropyl ether, diethyl ether and the like).

In producing polymers containing groups represented by Formula 8 it is desirable, particularly Where the hydrocarbonoxy groups represented by OR are of relatively high molecular weight, to accelerate the rate of the hydrolysis and condensation reaction by employing a catalyst. By way of illustration, from about 0.5 to 3 percent by weight (based on the water reacted) of an inorganic acid (such as hydrochloric acid or sulfuric acid) can be used as a catalyst.

The polymers of this invention that contain groups that are represented by Formula 8 can be isolated by conventional means. Thus, after completion of the hydrolysis and condensation, low boiling materials such as water, alkanol lay-products, solvents and the like can be removed from the reaction mixture by conventional means (e.g. distillation at reduced pressure) leaving the polymer as a residue.

It should be understood that polymers containing groups represented by Formula 8 are mixtures of compounds from which can be separated (e.g. by extraction or fractional crystallization) compounds containing only a particular type grouping (e. g. phosphorus combined only in P-OP or only in PO-Si linkages).

The polymers of this invention that contain groups represented by Formula 8 can also contain one or more groups represented by Formula 3. The latter groups are present in these polymers when silanes having the formula R,,Si(OR) Where R and x have above-defined meanings are cohydrolyzed and cocondensed along with the silanes or siloxanes of this invention in the produc-,

tion of the polymers. Alternately a group or represented by Formula 3 are present in the polymer if a starting siloxane of this invention is employed that contains a group or groups represented by Formula 3.

When siloxanes of this invention are employed in producing polymers containing groups represented by Formula 8, little or no SiOR or SiOH groups may be initially present to react to form ESiO-P linkages. However, ESlOSlE linkages in the siloxane can react with the waterand alcohol (i.e. the alcohol formed by the hydrolysis of P-OR) to produce SiOR and/ or SiOH. The presence of POH groups catalyzes such reactions of the normally stable Si--OSi linkage.

The compounds of this invention are useful as lubricants and as additives to lubricants for improving the lubricity thereof. In particular they can be added to organopolysiloxane lubricating fluids for imparting improved lubricity thereto. The siloxanes containing groups represented by Formula 2 and the polymers containing group represented by Formula 8 are also useful as flame and solvent resistant, protective coatings, particularly on groups metals such as steel, copper and aluminum. Such siloxanes and polymers can be formed in situ on the metal surface or canbe pro-formed and then applied as a dilute solution to the metal surface. After drying and curing the coating protects the metal even under severely corrosive, wet and dry conditions.

The following examples illustrate the present invention:

Example 1 One mole (221 4 grams) of gamma-aminopropyltriethoxysilane and one mole of triethylamine were added to a three necked flask fitted with stirrer, condenser and dropping funnel. One mole (228.5 grams) of was added to the dropping funnel. The (C H O) P (O)Cl was added slowly over a period of about 1 hour to the mixture of gamma-aminopropyltriethoxysilane and triethylamine with vigorous stirring. The reaction was immediate and exothermic. The temperature increased from 26 C. to 98 C. Triet'hylamine hydrochloride precipitated out immediately. The rate of addition of .Was such that the temperature did not exceed 100 C. at any time. After addition was completed the flask and contents were cooled to room temperature and the amine hydrochloride was removed by filtration. A total of 134 grams ,of triethylamine hydrochloride was removed. There was so produced as a filtrate a 65 percent yield (266 grams) of the product having the formula having an index of refraction, N of 1.4336 and having a pH of 6 to 7. The product was a pale yellow liquid. 7

The following elemental analysis for carbon, hydrogen, phosphorus and nitrogen and infra-red analysis confirmed the composition and structure of the product. a

One mole (221 grams) of gamma-aminopropyltriethoxysilane and 1 mole (101 grams) of triethylamine were charged to a kettle fitted'with a stirrer, condenser and dropping funnel. One mole (172.5 grams) of V 7 (Cz 5 )2 was charged to the dropping funnel. The

was added slowly over a period of about 20 minutes to the kettle with stirring. The temperature increased from about 26 C. and did not exceed 120 C. Triethylamine hydrochloride precipitated out immediately. Afteraddition was complete the reaction mixture was stirred for an additional lO'minutes. The reaction mixture then was filtered hot (about C.). The filtrate thus obtained was cooled to room temperature and filtered again. A total of 135 grams of triethylamine hydrochloride was removed by filtration; There was produced as a filtrate a 75 percent yield (285 grams) of clear, liquid product, having the formula: '(C H O) P(O)NH (CH Si(OEt) having an index of refraction, (N of 1.4293 and having a pH of about 6. The following elemental analysis for carbon,

hydrogen, silicon, phosphorus and nitrogen and infra-red analysis confirmed the indicated structure of the product} Elemental Analysis (wt-percent) C Si P N H TheoreticaL i ound Example 3 To a 500 cc., four necked flask equipped with a thermometer, stirrer, reflux condenser and a dropping funnel (all protected from the atmosphere with drierite tubes) were charged 0.l5 1 mole (31.0 grams) of delta-aminobutyl(rnethyl)diethoxysilane, 0.151 mole (15.5 grams) of triethylamine and 100.grams of anhydrous ethyl ether. The dropping funnel was charged with 0.151 mole (34.5 grams) of (C H O) P(O)Cl. The (C4H O) P(O)Cl was added slowly over a period of about 9 minutes to the flask with vigorous stirring. 'The flask and contents were maintained at 0 C. through the addition by means of a Dry Ice-acetone bath. Triethylamine hydrochloride precipitated during the addition. After completion of addition the flask and contents were maintained at 0 C. for an additional 15 minutes. After this time the reaction mixture was allowed to warm to 25 C. and was stirred at this temperature for 6.5 hours. After standing overnight the reaction mixture was cooled to 0 C. and filtered. The filtrate was cooled to 25 C. and filtered again. The filtrate was stripped at 100 C. at 1.0 mm. of Hg. A clear, pale yellow, liquid product having an index of refraction, N of 1.4410 was obtained in a 53 gram yield. This product was analyzed for phosphorus, nitrogen, carbon and hydrogen and was confirmed as having the formula:

Elemental Analysis (wt.-percent) O Si P N H Theoretical- -i ound one mole of (C H OP(O)Cl and one mole of triethylamine are dissolved in toluene and the solution is heated 9 for 0.5 hour at 100 C. there is produced a solution which can be filtered and stripped of toluene to produce a siloxane of this invention having the formula:

as a residue.

The formula of this compound can be confirmed by standard infrared and elemental analysis and cryoscopic molecular weight determinations.

Example 5 When 3.0 moles of a silane of this invention that is represented by the formula:

is dissolved in toluene and the solution so formed is mixed with 1.5 moles of water containing one percent by Weight of hydrochloric acid and the mixture so formed is maintained at 20 C. with stirring for about two hours, there is produced a polymer of this invention composed of groups having the formula:

The formula of this polymer can be confirmed by standard infrared and elemental analysis and cryoscopic molecular weight determinations.

Example 6 When five parts by weight of either a siloxane of this invention (e.g. the siloxane produced as described in Example 4) or a polymer of this invention (e.g. the polymer produced as described in Example 5) is dissolved in 109 parts by weight of toluene and the solution so formed is sprayed on a steel surface according to conventional coating techniques, there is produced, upon volatilization of the toluene,.a coating on the steel surface which protects the steel surface from corrosion.

Example 7 Following the above-described process, a siloxane of this invention having the formula: (C H O) P(O)NH(CH Si(CH 08i a)2( 2)3 2 92 is produced by reacting (C H O) P Cl and H N (CH Sl (CH 2 What is claimed is: 1. A hydrocarbonoxysilane represented by the formula:

0 n n (n o) i 1 IR" s i(o R)3n wherein R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R is a divalent hydrocarbon group containing at least three carbon atoms, n is an integer from O to 2 inclusive and the nitrogen atom is interconnected to silicon through at least three carbon atoms.

2. The hydrocarbonoxysilane of claim 1 wherein the group represented by R is a hydrocarbon group containing from 1 to 18 carbon atoms and R" is an alkylene group containing from 3 to 5 carbon atoms.

3. The hydrocarbonoxysilane of claim 1 wherein R is a hydrogen atom and R" is an alkylene group containing from 3 to 5 carbon atoms.

4. The hydrocarbonoxysilane of claim 1 wherein R" is an alkylene group containing from 3 to 5 carbon atoms and n is 0.

5. The hydrocarbonoxysilane of claim 1 wherein R" is an alkylene group containing from 3 to 5 carbon atoms and n is 1.

6. The hydrocarbonoxysilane of claim 1 wherein R" is an alkylene group containing from 3 to 5 carbon atoms and n is 2.

7. A hydrocarbonoxysilane represented by the formula:

8. A hydrocarbonoxysilane represented by the formula:

( 2 5 z NH 2) s 2 5 a 9. A hydrocarb onoxysilane represented by the formula It A siloxane comprising polymeric units represented by the formula:

wherein R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydro gen atom and the monovalent hydrocarbon groups, R" is a divalent hydrocarbon group containing at least three carbon atoms, n is an integer from 0 to 2 inclusive and the nitrogen atom is interconnected to silicon through at least three carbon atoms and (b) groups represented by the formula:

R,si0

wherein R has the above-defined meaning and x has a value from 0 to 3 inclusive.

12. The siloxane of claim 10 wherein R is a hydrocarbon group containing from 1 to 18 carbon atoms and R" is an alkylene group containing from 3 to 5 carbon atoms.

13. The siloxane of claim 10 wherein R is a hydrogen atom and R" is an alliylene group containing from 3 to 5 carbon atoms.

14. The siloxane of claim ltl wherein R" is an alkylene group containing from 3 to 5 carbon atoms and n is 0.

15. The siloxane of claim 10 wherein R" is an .alkylene group containing from 3 to 5 carbon atoms and n is 1.

16. The siloxane of claim 10 wherein R" is an alkylene group containing from 3 to 5 carbon atoms and n is 2.

17. The siloxane of claim 10 wherein R is a methyl group.

18. A polymer comprising polymeric units represented by the formula:

i i" i o I-N-RSi0 wherein R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R is a divalent hydrocarbon group containing :at least three carbon atoms, n is an integer from to 2 inclusiveand each "nitrogen atom is interconnected to silicon through at least three carbon, atoms; each phosphor-us atom and each silicon atom is bonded through oxygen to a member selected from the group consisting of phosphorus and silicon of another group represented by said formula.

19. The polymer of claim 18 wherein R is ahydrogen atom, R is, an alkylene group containing from 3 to 5 carbon atoms and n is 0.

20. The polymer of claim 18 wherein R is a hydrogen atom, R" is an alkylene group containing from 3 to 5 carbon atoms and n is 1.

21. The polymer of claim 18 wherein R is a hydrogen atom, R. is an alkylene group containing frorn3 to 5 carbon atoms and n is 2.

22. A process for producing a hydrocarbonoxysilane represented by the formula:

wherein R is a monovalent hydrocarbon group, R is a I wherein 'X is a halogen atom and R has the above- ;defined meaning and (II) a silane having the formula:

wherein R, R, R", and n have the above-defined meanings. f

'23. A process for producing a siloxane comprising groups represented by the formula:

wherein R'isamonovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R" is a divalent hydrocarbon group containing at least three carbon atoms, n is an integer'from 0 to 2 inclusive wherein X is a halogen atom and R has the abovedefined meaning and (II) a siloxane comprising groups having the formula:

wherein'R, R, R, and n have the above-defined meanings. 1

24. A process for producing the polymer of claim 18 which comprises hydrolyzing and condensing a hydro carbonoxysilane represented by the formula:

wherein R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen -atom and the monovalent hydrocarbon groups, R is a divalent hydrocarbon group, n is an integer from 0 to 2 inclusive and the nitrogen atom is interconnected to silicon through at least three carbon atoms.

25. A process for producing the polymer of claim 18 which comprises hydrolyzing and condensing a siloxane comprising groups represented by the formula:

* r r (R0) PN-R"'s1o 2 V Wherein R is a monovalent hydrocarbon group, R is a member selected from the group consisting of the hydrogen atom and the monovalent hydrocarbon groups, R" is a divale'nt hydrocarbon group, n is an integer from 0 to 2 inclusive'and the nitrogen atom is interconnected to silicon through at least three carbon atoms.

References Cited .by the Examiner UNITED STATES PATENTS MURRAY TILLMAN, Primary Examiner.

MILTON STERMAN, HAROLD N. BURSTEIN, WILLIAM H. SHORT, Examiners. 

10. A SILOXANE COMPRISING POLYMERIC UNITS REPRESENTED BY THE FORMULA: 